CN101481343A - Method for synthesizing N,N-diethylamino ethanethiol - Google Patents
Method for synthesizing N,N-diethylamino ethanethiol Download PDFInfo
- Publication number
- CN101481343A CN101481343A CNA2009103004732A CN200910300473A CN101481343A CN 101481343 A CN101481343 A CN 101481343A CN A2009103004732 A CNA2009103004732 A CN A2009103004732A CN 200910300473 A CN200910300473 A CN 200910300473A CN 101481343 A CN101481343 A CN 101481343A
- Authority
- CN
- China
- Prior art keywords
- diethylamino ethanethiol
- synthetic method
- diethylamine
- ethanethiol
- diethylamino
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 12
- JOBAOCJQNOWKPH-UHFFFAOYSA-N 1-(diethylamino)ethanethiol Chemical compound CCN(CC)C(C)S JOBAOCJQNOWKPH-UHFFFAOYSA-N 0.000 title abstract 3
- 230000002194 synthesizing effect Effects 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical compound C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 0.000 claims abstract description 22
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010189 synthetic method Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- YBDSNEVSFQMCTL-UHFFFAOYSA-N 2-(diethylamino)ethanethiol Chemical compound CCN(CC)CCS YBDSNEVSFQMCTL-UHFFFAOYSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 9
- 230000000630 rising effect Effects 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 150000002170 ethers Chemical class 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- -1 sulphur hydrogen salt Chemical class 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- PQLFROTZSIMBKR-UHFFFAOYSA-N ethenyl carbonochloridate Chemical compound ClC(=O)OC=C PQLFROTZSIMBKR-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- UURAUHCOJAIIRQ-QGLSALSOSA-N tiamulin Chemical compound CCN(CC)CCSCC(=O)O[C@@H]1C[C@@](C)(C=C)[C@@H](O)[C@H](C)[C@@]23CC[C@@H](C)[C@]1(C)[C@@H]2C(=O)CC3 UURAUHCOJAIIRQ-QGLSALSOSA-N 0.000 description 2
- 229960004885 tiamulin Drugs 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- ZXYFGZNMDRNOGQ-UHFFFAOYSA-N ac1lawgt Chemical compound [S]O ZXYFGZNMDRNOGQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a synthetic method for N, N-diethylaminoethanethiol, comprising the following step: the N, N-diethylaminoethanethiol is prepared after mixing ethylene sulfide and diethylamine under the condition of adding catalyst and heating the mixture to 50-80 DEG C for reaction. In the method, under the condition of presence of the catalyst, the raw materials can fully react without using any solvent and the ethylene sulfide can be effectively prevented from self polymerization, thus obtaining the products with high yield and quality. Meanwhile, without producing the three wastes, the method effectively protects the environment.
Description
Technical field
The present invention relates to a kind of synthetic method of compound, relate in particular to a kind of N, the synthetic method of N diethylamino ethanethiol.
Background technology
N, N diethylamino ethanethiol are the key intermediates of producing sterilant Tiamulin for animals, because the domestic and international market of Tiamulin enlarges gradually in recent years, so intermediate N, the demand of N diethylamino ethanethiol also increases thereupon, about 250 tons/year.According to the record of domestic and foreign literature, have six operational paths in the prior art, be respectively Vinyl chloroformate route, sulphur hydrogen salt route, thiocyanate-route, benzyl sulfhydrate route, thiocarbamide route and thiirane route.
Wherein, the Vinyl chloroformate route is as follows:
This method route is long, and uses hypertoxic tubing products hydroxyl sulfur alcohol, therefore be difficult for obtaining, and quality product is impure.
Sulphur hydrogen salt route is as follows:
Though this method route is short, product that obtains and Sodium sulfhydrate generation polymerization, so the yield of product is low.
The thiocyanate-route is as follows:
This method route is long, and the yield of product is low, and by product is more, and product is difficult for purifying;
The benzyl sulfhydrate route is as follows:
This method will be reduced under very low temperature through sodium Metal 99.5 and be obtained product, and severe reaction conditions is unfavorable for suitability for industrialized production.
The thiocarbamide route is as follows:
This method reaction scheme is long, produces a large amount of alkaline waste water contaminate environment.
The thiirane route is as follows:
This method is synthesized N with thiirane and diethylamine by compressive reaction, the N diethylamino ethanethiol, and need in organic solvent, react, solvent load is big, it is big to reclaim power consumption, and is difficult to avoid the thiirane self-polymerization to become white solid, finally causes poor product quality, yield low.
Summary of the invention
Technical problem to be solved by this invention is the shortcoming that exists at above six technologies, provides a kind of N, the synthetic method of N diethylamino ethanethiol.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of N, the synthetic method of N-diethylamino ethanethiol, this method comprises: under the condition that adds catalyzer, after thiirane and diethylamine mixing, be heated to 50 ℃～80 ℃ reactions and make N, the N diethylamino ethanethiol.
The invention has the beneficial effects as follows: under the condition that catalyzer exists; can not use any solvent just can make raw material reaction complete, and can effectively stop the thiirane self-polymerization, thereby obtain high yield, high-quality product; this technology does not produce the three wastes simultaneously, effectively protects environment.
On the basis of technique scheme, the present invention can also do following improvement.
Further, in reaction unit, add earlier thiirane and stir, add diethylamine and catalyzer again after, it is stirred, and can make N, the N-diethylamino ethanethiol in 50 ℃～80 ℃ following temperature rising reflux reactions.
Further, after the reaction of stirring temperature rising reflux finished, diethylamine and catalyzer were reclaimed in distillation, and underpressure distillation can make N again, the N diethylamino ethanethiol.
Further, described reaction unit is a reactor.
Further, the reaction times of described temperature rising reflux is 10 hours～15 hours.
Further, the consumption of described thiirane is 1:1～1:10 with the ratio of the consumption of diethylamine.
Further, described catalyzer is a boiling point greater than 60 ℃ ethers.
Further, described ethers is a sherwood oil.
Further, described catalyzer is a sodium borohydride.
Further, described catalyst consumption is to account for 0.5%～10% of thiirane and diethylamine total mass.
Embodiment
Below in conjunction with accompanying drawing principle of the present invention and feature are described, institute gives an actual example and only is used to explain the present invention, is not to be used to limit scope of the present invention.
The present invention adds a certain amount of thiirane earlier and stirs in 500 liters～2000 liters reactor, the diethylamine that adds 1 times to 10 times of thiirane quality again, after then adding accounts for 0.5%～10% catalyzer of thiirane and diethylamine total mass, it is stirred, and in 50 ℃～80 ℃ following temperature rising reflux reactions 10 hours～15 hours, reaction finishes to distill and reclaims diethylamine and catalyzer, and underpressure distillation can make N again, the N diethylamino ethanethiol.Described catalyzer is a boiling point greater than 60 ℃ ethers or sodium borohydride.The preferred ethers catalyzer of the present invention is a sherwood oil.
Reaction equation of the present invention is:
The present invention is by adding catalyzer; can effectively stop the thiirane self-polymerization and with the polymerization of product; and thiirane can not use the just direct and diethylamine reaction of any solvent; make raw material reaction complete; thereby the acquisition yield reaches more than 95% and mass percent concentration can reach 99% product; this technology does not produce the three wastes simultaneously, effectively protects environment.
Below with two embodiment to N of the present invention, the synthetic method of N-diethylamino ethanethiol is described in further detail.
Embodiment one:
Elder generation adds 60 kilograms thiirane and stirs in 500 liters reactor, the diethylamine that adds 180 kilograms again, after then adding 2 kilograms sherwood oil, it is stirred, and in 60 ℃ of following temperature rising reflux reactions 10 hours, reaction finishes to distill and reclaims diethylamine and sherwood oil, and underpressure distillation can make 107 kilograms N again, the N-diethylamino ethanethiol.
The reaction equation of present embodiment is:
The N of present embodiment, the mass percent concentration of N-diethylamino ethanethiol are 99%, and yield can reach 95.5%.
Embodiment two:
Elder generation adds 240 kilograms thiirane and stirs in 2000 liters reactor, the diethylamine that adds 1200 kilograms again, after then adding 4 kilograms sodium borohydride, it is stirred, and in 55 ℃ of following temperature rising reflux reactions 15 hours, reaction finishes to distill and reclaims diethylamine and sodium borohydride, and underpressure distillation can make 435 kilograms N again, the N diethylamino ethanethiol.
The N of present embodiment, the mass percent concentration of N diethylamino ethanethiol are 99%, and yield can reach 96.4%.
The reaction equation of present embodiment is:
The above only is preferred embodiment of the present invention, and is in order to restriction the present invention, within the spirit and principles in the present invention not all, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
- [claim 1] a kind of N, the synthetic method of N-diethylamino ethanethiol is characterized in that: this method comprises: under the condition that adds catalyzer, after thiirane and diethylamine mixing, be heated to 50 ℃～80 ℃ reactions and make N, the N diethylamino ethanethiol.
- [claim 2] N according to claim 1, the synthetic method of N-diethylamino ethanethiol, it is characterized in that: elder generation adds thiirane and stirs in reaction unit, after adding diethylamine and catalyzer again, it is stirred, and can make N, the N-diethylamino ethanethiol in 50 ℃～80 ℃ following temperature rising reflux reactions.
- [claim 3] N according to claim 2, the synthetic method of N-diethylamino ethanethiol is characterized in that: after the reaction of stirring temperature rising reflux finished, diethylamine and catalyzer were reclaimed in distillation, and underpressure distillation can make N again, the N diethylamino ethanethiol.
- [claim 4] N according to claim 3, the synthetic method of N-diethylamino ethanethiol is characterized in that: described reaction unit is a reactor.
- [claim 5] N according to claim 3, the synthetic method of N-diethylamino ethanethiol is characterized in that: the reaction times of described temperature rising reflux is 10 hours～15 hours.
- According to the arbitrary described N of claim 1～3, the synthetic method of N-diethylamino ethanethiol is characterized in that [claim 6]: the consumption of described thiirane is 1:1～1:10 with the ratio of the consumption of diethylamine.
- According to the arbitrary described N of claim 1～3, the synthetic method of N-diethylamino ethanethiol is characterized in that [claim 7]: described catalyzer is a boiling point greater than 60 ℃ ethers.
- [claim 8] N according to claim 7, the synthetic method of N-diethylamino ethanethiol is characterized in that: described ethers is a sherwood oil.
- According to the arbitrary described N of claim 1～3, the synthetic method of N-diethylamino ethanethiol is characterized in that [claim 9]: described catalyzer is a sodium borohydride.
- According to the arbitrary described N of claim 1～3, the synthetic method of N-diethylamino ethanethiol is characterized in that [claim 10]: described catalyst consumption is to account for 0.5%～10% of thiirane and diethylamine total mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910300473A CN100593537C (en) | 2009-02-18 | 2009-02-18 | Method for synthesizing N,N-diethylin ethanethiol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910300473A CN100593537C (en) | 2009-02-18 | 2009-02-18 | Method for synthesizing N,N-diethylin ethanethiol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101481343A true CN101481343A (en) | 2009-07-15 |
| CN100593537C CN100593537C (en) | 2010-03-10 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910300473A Active CN100593537C (en) | 2009-02-18 | 2009-02-18 | Method for synthesizing N,N-diethylin ethanethiol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100593537C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153494A (en) * | 2011-03-04 | 2011-08-17 | 赵云现 | Synthesis technology for N,N-diethylamino group ethanethiol |
| CN104774164A (en) * | 2015-02-16 | 2015-07-15 | 张丽学 | Preparation process for 2-diethylaminoethanethiol |
| CN105152990A (en) * | 2015-07-30 | 2015-12-16 | 宁夏泰瑞制药股份有限公司 | Preparation method for diethylaminoethanethiol |
| CN104447449B (en) * | 2014-12-30 | 2016-06-15 | 陕西师范大学 | The method of one pot process taimulin |
| CN112812026A (en) * | 2020-12-30 | 2021-05-18 | 茂名云龙工业发展有限公司 | Method for producing N, N-diethylamino isopropanol |
| CN113372248A (en) * | 2021-06-11 | 2021-09-10 | 保定北瑞甾体生物有限公司 | Process for preparing thiols |
| CN114315665A (en) * | 2021-12-16 | 2022-04-12 | 保定加合精细化工有限公司 | Preparation method of 2-diethylaminoethanethiol and application of impurities thereof |
-
2009
- 2009-02-18 CN CN200910300473A patent/CN100593537C/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153494A (en) * | 2011-03-04 | 2011-08-17 | 赵云现 | Synthesis technology for N,N-diethylamino group ethanethiol |
| CN104447449B (en) * | 2014-12-30 | 2016-06-15 | 陕西师范大学 | The method of one pot process taimulin |
| CN104774164A (en) * | 2015-02-16 | 2015-07-15 | 张丽学 | Preparation process for 2-diethylaminoethanethiol |
| CN105152990A (en) * | 2015-07-30 | 2015-12-16 | 宁夏泰瑞制药股份有限公司 | Preparation method for diethylaminoethanethiol |
| CN105152990B (en) * | 2015-07-30 | 2017-03-22 | 宁夏泰瑞制药股份有限公司 | Preparation method for diethylaminoethanethiol |
| CN112812026A (en) * | 2020-12-30 | 2021-05-18 | 茂名云龙工业发展有限公司 | Method for producing N, N-diethylamino isopropanol |
| CN113372248A (en) * | 2021-06-11 | 2021-09-10 | 保定北瑞甾体生物有限公司 | Process for preparing thiols |
| CN114315665A (en) * | 2021-12-16 | 2022-04-12 | 保定加合精细化工有限公司 | Preparation method of 2-diethylaminoethanethiol and application of impurities thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100593537C (en) | 2010-03-10 |
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Effective date of registration: 20151102 Address after: 071254, Mancheng County, Mancheng County, Hebei City, Baoding Province Patentee after: BAODING JIUFU BIOCHEMICAL CO., LTD. Address before: 071000 Room 601, Kangtai building, 728 West Yuhua Road, Hebei, Baoding Patentee before: Zhao Yunxian |
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Address after: 071254 Yu Jia Zhuang Xiang Pang Cun, Mancheng County, Baoding City, Hebei Province Patentee after: Hebei Yuanda Jiufu Biotechnology Co.,Ltd. Address before: 071254 Yu Jia Zhuang Xiang Pang Cun, Mancheng County, Baoding City, Hebei Province Patentee before: BAODING JIUFU BIOCHEMICAL Co.,Ltd. |